Process for one-bath dyeing and printing of textile material

ABSTRACT

PROCESS FOR THE ONE-BATH DYEING AND PRINTING OF TEXTILE MATERIAL MADE OF SYNTHETIC OR NATURAL FIBERS OR MIXTURES OF SUCH FIBERS, WITH APPROPRIATE DYESTUFFS ACCORDING TO A CONTINUOUS OR SEMI-CONTINUOUS PAD-DYEING OR PRINTING METHOD BY APPLYING TO THE MATERIAL A PADDING LIQUOR OR A PRINTING PASTE CONTAINING AN ORGANIC SOLVENT, ONE OR MORE ORGANIC DYESTUFFS, IF REQUIRED A CHEMICAL AGENT FOR THE FIXATION OF THESE DYESTUFFS, WATER AND A PHOSPHINE OXIDE AND/OR AN AMINE OXIDE, AND SUBJECTING THE DYED MATERIAL OPERATION, TO THE ACTION OF HEAT BELOW THE SOFTENING POINT OF THE FIBROUS MATERIAL OR ALLOWING IT TO DWELL AT ROOM TEMPERATURE OR AT A MEDERATELY ELEVATED TEMPERATUTURE, FOR THE FIXATION OF THE DYESTUFF ON THE FIBER.

United States Patent US. Cl. 8-163 15 Claims ABSTRACT OF THE DISCLOSURE Process for the one-bath dyeing and printing of textile material made of synthetic or natural fibers or mixtures of such fibers, with appropriate dyestuffs according to a continuous or semi-continuous pad-dyeing or printing method by applying to the material a padding liquor or a printing paste containing an organic solvent, one or more organic dyestuffs, if required a chemical agent for the fixation of these dyestuffs, water and a phosphine oxide and/ or an amine oxide, and subjecting the dyed material thus" treated, optionally after an intermediate drying operation, to the action of heat below the softening point of the fibrous material or allowing it to dwell at room temperature or at a moderately elevated temperature, for the fixation of the dyestuif on the fiber.

' The present invention relates to a process for the onebath dyeing and printing of textile material.

' The continuous dyeing of textile material of various fiber types with dyestuffs or diiferent chemical classes from an aqueous liquor has already been known for years and has since been used in practice to a large extent. For the same purpose, detailed disclosure has also lately been made in the art on the use of organic solvents or mixtures of organic solvents with each other or with water as dyeing media.

This invention now relates to the one-bath dyeing and printing of textile material made from synthetic or natural fibers or blends of such fibers with suitable dyestuffs according to a continuous or semi-continuous padding or printing method, which comprises applying to the material a padding liquor or a printing paste containing an organic solvent, one or more organic dyestuffs, if required a chemical agent for the fixation of these dyestuffs, Water and a phosphine oxide of the general formula 1) and/or an amine oxide of the general formula (2) 0 R1 0 R1 R-i Riq in' which R, R and R each stands for an unbranched or branched alkyl or alkenyl group of 1 to 18 carbon atoms, which may be substituted by hydroxy, cyano or amino groups or by halogen atoms and which may be interrupted by oxygen, sulfur and/or nitrogen atoms and/or by a carbonyloxy, carbamoyl or sulfamoyl group, and the radicals R and R may constitute together with the central phosphorus or nitrogen atom a heterocyclic 5- or 6-membered ring, with the proviso that the sum of all carbon atoms contained in R, R and R is at least 8 and at most 20, and subjecting the material thus treated, optionally after an intermediate drying operation, to the action of heat below the softening point of 3,814,579 Patented June 4, 1974 the fibrous material or allowing it to dwell at room temperature or at slightly elevated temperature, for fixing the dyestufi on the fiber.

The instant process differs from methods known in this field in that the dyeing media consisting of mixtures of water with organic solvents also contain phosphine oxides and/or amine oxides of .the above-mentioned chemical constitution specified by the formulae given above, which have polyfunctional properties that exert a favorable influence on the dyeing and printing operations of the invention as well as on the dyed products resulting therefrom:

For example, the above-cited phosphine oxides and/or amine oxides may be used to prepare dyeing liquors which, depending on the solvent used and on the amounts of product and water employed, provide clear solutions or emulsions or emulsified dispersions of low, medium or high viscosity. Seen from a practical point of view, this effect of the substances both as emulsifiers and as thickeners means that the problems that occur in dyeing because of material and machinery, can be overcome also by an addition of these products.

In addition to the property of the cited adjuvants of homogeneously distributing determined amounts of water or aqueous dyestufi solutions or dispersions in organic sol-vents which are not miscible with water, the solubilizing effect of the products also allows the process of the invention to use such dyestuffs in a dissolved form which are usually considered insoluble as well in the organic solvent used as in water.

Hence, using the phosphine oxides and/or amine oxides, it is possible according to this invention to achieve the aforementioned effects by means of only one adjuvant alone, whereas the known methods require several products having specific properties.

According to the process of the invention, the dye stuff preparation is applied to the textile material, preferably by pad-dyeing, but also by spraying, doctoring and other techniques that assure a continuous operation, for example printing. The pad-dyeing operation is generally performed at room temperature but it may also be carried out at any lower or higher temperature ranging from the freezing point to the boiling point of the solvent mixture used or of the azeotropic mixture that may result therefrom. If, however, high-viscosity dyeing liquors are to be used, for example to prevent migration, the temperature applied should be about room temperature, or a laboratory test should previously be made to determine the maximum temperature at which the thickened emulsion is still stable.

After impregnation, preferably pad-dyeing, of the textile materials with the dyeing liquors or printing pastes the dyeings or prints are subjected to a suitable fixation method which depends on the dyestuffs used.

For the fixation of the dyestuffs thus applied by the action of heat, there are now various methods available:

For example, the material which has been padded or printed with the dyestuif preparation may be subjected immediately afterwards in moist state to a steaming or pressure-steaming process, optionally using superheated steam or solvent vapor (one-bath pad Wet-steaming process). It is also possible to steam under the conditions mentioned above the pad-dyeings or prints'after an intermediate drying operation at relatively low temperatures of up to a maximum of C. (one-bath pad steam process) or to thermosol them on a tenter frame or a perforated drum drier by sucking dry hot air through them or by means of contact heat (thermofixation process). Intermediate drying after padding or printing is, however, not required if the dyestuff fixation is brought about together with the drying operation by treating the dyed material, for example, on a hotflue (one-bath pad drying process). When the dyestuff is fixed by means of dry heat, the temperature chosen has to be adapted to the dyed material present, such as to keep below the softening point of the fibrous material. The various possibilities of a heat fixation according to the present invention, as referred to above, especially offer the advantage of a continuous operation in the case of a one-bath process. These methods assure very high dyeing rates and a very good reproducibility of the dyeing results.

The favorable conditions of one-bath dyeing are preserved by batching up the textile articles, which have been padded or printed with the dyestuif preparation, and allowing the fibrous material to dwell in moist state on a skein at room temperature or at a moderately elevated temperature of from 30 to 60 C. for 2 to 24 hours, preferably for 4 to 14 hours (one-bath pad-batch or pad short-dwell process). This semi-continuous technique is characterized by a high economy of operation, due to the saving of energy, and does not require expensive intermediate-drying and fixing apparatuses.

Depending on the dyestuffs used and on the color intensity, fixation may be followed by an after-cleaning operation, for which the phosphine oxides and/or amine oxides mentioned may also be used in the aqueous or solvent-containing after-treatment liquor.

The process of the present invention is suitable for the continuous or semi-continuous dyeing and printing of various fiber types of synthetic or natural origin, for example of woven or knit fabrics, combed material, cables and nonwovens (fleeces) made of polyester, polyamide, polyurethane, polyacrylonitrile, cellulose-2 /2-acetate, cellulose-triacetate, polyvinyl chloride, polyvinyl alcohol, polypropylene or cellulose fibers or wool or of blended materials of these fibers.

As organic solvents suitable for the process of the invention, there are especially used hydrocarbons and, in particular, halogenated, especially chlorinated, hydrocarbons, particularly perchloroethylene (tetrachloroethylene), trichloroethylene, trichloroethane, tetrachloroethane, methylene chloride, chloroform, carbon tetrachloride, fluorotrichloromethane or trifiuorotrichloroethane. There may, however, also be used benzene, chlorobenzene, cyclohexane or gasolines as well as mixtures thereof which may boil while forming azeotropic mixtures. The mixing ratio of organic solvent to water in the dyeing liquors and printing pastes ranges from 1-99, preferably 30-98% by volume of organic solvent to 99-1, preferably 702% by volume of water.

Amongthe phosphine oxides of formula (1) and the amine oxides of formula (2) to be used according to the invention, there may, for example, be mentioned the following compounds:

Octyl-dimethyl-phosphine oxide, octyl diethyl phosphine oxide, decyl-dimethyl-phosphine oxide, decyl-methyl-butyl-phosphine oxide, dodecyl-dimethyl-phosphine oxide, dodecyl-diethyl-phosphine oxide, -palmitic acidamidomethyl-dimethyl-phosphine oxide, -palrnitic acidamindopropyl-dimethyl-phosphine oxide, hexyl methylbutyl-phosphine oxide( hexyl-dimethyl-phosphine oxide, octyl-dimethyl-amine oxide, N dodecyl piperidine-N- oxide, tetradecyl-dimethyl-amine oxide, coco fatty aciddimethyl-amine oxide, oleoyl-amido-methyl dimethylamine oxide or hexadecyl-bis (fi-hydroxy-ethyD-amine oxide.

The phosphine oxides and amine oxides are used, according to the invention, either as such or in mixture with each other in amounts of from 1 to 100 g./l., preferably from 3 to 60 g./l., calculated on the mixture of organic solvent and water.

For the preparation of the dyeing liquors, it is most advantageous according to the invention to proceed in the following manner:

The phosphine oxides or amine oxides mentioned under formulae (1) and (2) or mixtures of these products are first dissolved in an organic solvent, preferably at room temperature. Where required, water-insoluble dyestufls, for example of the disperse dyestuff type, may also be dissolved in this solution. This dyestuff type comprises not only dyestuifs which have a good solubility in theorganic solvent used without an addition of the adjuvants of the invention but also a large number of dyestuffs which are usually not, or only sparingly, soluble in the organic solvent used but can be solubilized or substantially improved in their solubility using the cited products offormulae (1) and (2). I

Alternatively, water-soluble dyestufls are dissolved in the water portion of the padding liquor or water-insoluble dye-stuffs are also dispersed therein at a temperature of from room temperature to 0., preferably from 40 to 60 C. This aqueous solution or dispersion is then slowly added while stirring to the solution of the phosphine oxides and/or amine oxides and, where required, of dyestuffs, in an organic solvent. Depending on the organic solvents used and on the amounts of adjuvants and water chosen, the results are from clear solutions up to low-viscosity and high-viscosity emulsions or emulsified dispersions. H The process of the invention is practically suitable for any dyestuff class which can also be applied from an aqueous liquor, for example disperse dyestuffs, vat dye stuffs, reactive dyestuffs, acid dyestuffs, metal complex dyestuffs, chroming dyestuffs, substantive dyestuffs, leuco esters of vat dyestuffs, cationic dyestuffs, developing dye stuffs and the like. Chemical agents which may be requiredfor the fixation of some dyestuffs when dyeing from an aqueous liquor, for example alkaline agents in the dyeing of cellulosic fibers with reactive dyestuffs, are added while stirring to the dyeting liquors in a water-diluted form, most advantageously immediately before application will be started. The following Examples illustrate the invention (by giving a survey of the variety of possible applications offered by the instant process as regards dyestuff classes and fibrous materials to be used), the parts and percentages being by weight unless stated otherwise and the names and C.I.-numbers of the dyestuffs used according to. the invention originating from Color Index, 2nd edition, 1956, vol. 3.

EXAMPLE 1 50 g. of decyl-dimethyl-phosphine oxide were dissolved in 810 ml. of perchloroethylene at about 25 C. In ad: dition, a second solution of 2.7 g. of the dyestulf fSolubilized Vat Violet 2, C.I.-No. 73386, in ml. of Water was prepared at about 90 C. This second aqueous solution was then slowly added while continuously stirring to the perchloroethylene solution and the mixture was stirred until it had cooled to room temperature, whereupon a rather viscous emulsion was obtained. Subse: quently, 0.9 g. of ammonium sulfate and 0.6 g. of sodium formiate were dissolved in 30 ml. of water at room temperature and the solution was also added while stirring to the emulsion that had been prepared previously.

A blended fabric made of 67% of polyester fibers and 33% of cotton was padded with the liquor thus prepared on a padding machine with a squeezing effect of about 90%, calculated on the weight of the dry material, and then dried. (Drying can be performedthis applies to all subsequent Examples-either in the air, in a conventional drying apparatus or in a special device which en-" ables the organic solvent used to be recovered). The dyestutf was then fixed on the textile material by a dry-heat treatment at 210 C. which took 60 seconds. A red-violet dyeing was obtained on both fiber types of the blended fabric. 9

Sirnilar tinctorial results were obtained using, according to the above dyeing method, the same amount of coco fatty acid-dimethyl amine oxide instead of decyl-dimethylphosphine oxide.

EXAMPLE 2 Agreen dyeing was obtained by treating a blended fabric made of 55 parts of polyester fibers and 45 parts of wool, under the application conditions of Example 1, with a padding liquor containing, in addition to the same composition of'perchloroethylene, water, ammonium sulfate and sodium formiate' as above, the same amount by weight of the compound Solubilized Vat Green 1, C.I.- No. 59826, as a dyestuif, 36 g. of coco fatty acid-dimethylamine oxide and 3.5 g. of sodium chlorate. For the fixation of the dyestutf, the padded material was thermosoled for 1 minute at 185 C.

EXAMPLE 3 25 g. of decyl-dimethyl-phosphine oxide were dissolved at room temperature in 820 ml. of perchloroethylene. Moreover, 7 g. of the dyestulf Basic Blue 3, C.I.-No. 51005, were dissolved in 180 ml. of water at about 70 C. After having cooled, the aqueous solution was slowly added while stirring to the perchloroethylene solution, whereupon a viscous emulsion was obtained.

A fabric made of polyacrylonitrile fibers was then padded on a padding machine with the dyeing liquor thus prepared. After having been dried, the material was steamed for about 30 minutes under a pressure of about 1 atmosphere gauge for the fixation of the dyestuif. A blue dyeing was obtained.

A similar tinctorial result could be obtained using, instead of the afore-mentioned textile material, a fabric made of acid-modified polyester fibers.

Analogous results could be obtained by performing dyestulf fixation on the two materials by means of a dryheattreatment for 1 minute at 210 C. instead of steammg.

EXAMPLE 4 4 g. of the 1:2-chromium complex compound of the dyestutf of the formula (a) a fabric made of polyamide-6,6 fibers, (b) a fabric made of wool and (c) a combed material made of polypropylene fibers.

After the padding and drying operations, the three fiber types were steamed for about 40 minutes at 100-101" C. to fix the dyestuif. In all three cases, grey dyeings were obtained on each of the substrates.

EXAMPLE 5 52g. of decyl-dimethyl-phosphine oxide were dissolved at room temperature in 800 ml. of perchloroethylene. Moreover, a solution of 4 g. of the dyestulf Direct Yellow 8, C.I.-No. 13920, in 200 ml. of water was prepared at 80 C. This second solution was then added while stirring to the perchloroethylene solution and the mixture was further stirred for some time, until cooled to room temperature.

The viscous emulsion thus obtained was then used to pad (a) a fabric made of cotton, (b) a fabric made of polyamide-6 fibers an (c) a fabric made of cellulose-2 At-acetate fibers fl; I

tained'on each of the three'textile materials. 4

- EXAMPLE 6 42 g. of decyl-dimethyl-phosphine oxide were dissolved at about 25 C. in 830 ml. of perchloroethylene. To the solution thus prepared, a solution heated to about 40 C. and containing 4 g. of the dyestuff Acid Red 42," C.I.- No. 17070, in 170 ml. of water was then slowly added while stirring. A blended fabric made of 50% of polyamide-6,6 fibers and 50% of wool was then padded on 8. padding machine with this padding liquor, then dried and finally steamed for about 30 minutes at 10010l C. A red dyeing was obtained on the two components of the blended fabric.

EXAMPLE 7 45 g. of decyl-dimethyl-phosphine oxide were mixed with 7 g. of the dyestutf Disperse Orange 13," C.I.-No. 26080, and the mixture was dissolved at about 25 C. in 770 ml. of perchloroethylene. Moreover, 4 g. of the dyestutf Reactive Blue 19, C.I.-No. 61200, were separately dissolved at about 90 C. in 180 ml. of water. This aqueous solution was then slowly added while stirring to the perchloroethylene solution and the mixture was further stirred until cooled to about 25 C. Subsequently, 50 ml. of an aqueous solution containing 50 g. of sodium bicarbonate per liter were also added to the dyebath.

A blended fabric made of 67% of polyester fibers and 33% of cotton was padded on a padding machine with the liquor prepared in this manner, then dried and thermosoled for 1 minute at 210 C. A bicolor dyeing was obtained on the blended fabric: an orange color on the polyester fiber portion and a blue color on the cellulosic fiber portion.

EXAMPLE 8 60 g. of decyl-dimethyl-phosphine oxide were dissolved in 920 ml. of benzene at room temperature. To this solution, ml. of an aqueous dyestutf solution containing, per liter, 30 g. of the dyestuff Basic Violet 2, C.I.-No. 42520, were slowly added while stirring.

A combed material made of polyacrylonitrile fibers was padded on a paddingmachine with the solution thus obtained, then dried and steamed for 30 minutes at 100- 101 C. A red-violet dyeing was obtained.

EXAMPLE 9 55 g. of decyl-dimethyl-phosphine oxide were dissolved at about 25 C. in 985 ml. of perchloroethylene. To this solution, 15 ml. of Water which was heated to about 60 C. and in which 0.5 g. of the dyestulf Basic Blue 3,? C.I.-No. 51005 was dissolved, were slowly added while stirring. f

A fabric made of acid-modified polyester 'fibers was padded on a padding machine with the solution thus prepared, and was dried. The dyestuff was fixed by means of a dry-heat treatment at 210 C. within 1 minute. A light blue dyeing was obtained. Y

EXAMPLE 10 v I 50 g. of decyl-dimethyl-phosphine oxide were dissolved at room temperature in 880 ml. of perchloroethylene. To

this liquor, ml. of an aqueous dyestufl. solution heated to about 40 C. and containing 2.5 g. of the dyestutf Solubilized Vat Orange 1, C.I.-No. 59106, were slowly added while stirring. Subsequently, 3 g. of sodium chlorate were dissolved in 30 ml. of water and the solution was also added while stirring to the dyebath.

A fabric made of"67% of polyester fibers and 33 of cotton was padded on a padding machine with the liquor obtained, dried and thermosoledfor 1 minute at 215 C. A yellow dyeing was obtained on the two components of the blended fabric.

\ EXAMPLE 11 7 g. of tetradecyl-dimethyl-phosphine oxide were dis-. solved at room temperature in 340 ml. of a gasoline having range of "from 80 to 100 C. 660 ml. of Water, in which 6 g. of the dyestulf Acid Red 42, C.I.-No. 17070, were dissolved, were slowly added while stirring continuously.

A fabric made of polyamide-6 fibers was padded on a padding machine with the emulsion thus obtained, dried and steamed for about 20 minutes at a pressure of about 1 atmosphere gauge. A red dyeing was obtained.

EXAMPLE 12 30 g. of decyl-dimethyl-phosphine oxide were dissolved at room temperature in 750 ml. of perchloroethylene. Moreover, a solution of g. of the dyestuif Reactive Yellow 17, C.I.-No. 18852, in 200 ml. of water was prepared at about 80 C. This aqueous dyestulf solution was then slowly added While stirring to the perchloroethylene solution and the mixture was further stirred until cooled to 25 C. Subsequently, 50 ml. of a 4% sodium hydroxide solution were also added to the dyebath.

' A cotton fabric was then padded on a padding machine with the liquor thus prepared and the moisture excess was squeezed 01f. The padded material was then batched up, wrapped with a plastic foil and allowed to dwell at this state for 4 hours at room temperature, in order to fix the dyestuif. Upon an after-washing operation usual for dyeings produced with reactive dyestuffs, using non-ionic detergents, a yellow dyeing on cotton was obtained.

We claim:

1. A process for the one-bath dyeing and printing of textile material made of synthetic or natural fibers or mixtures of such fibers, with appropriate dyestuffs according to a continuous 'or semi-continuous pad-dyeing or printing method, which comprises applying to the material a padding liquor or a printing paste containing an organic solvent, one or more organic dyestuffs, if required a chemical agent for the fixation of these dyestulfs, water and a phosphine oxide of the general formula (1) or an amine oxide of the general formula (2) 2 R1 g/Rl R-P R-N in which R, R and R each is unbranched or branched alkyl or alkenyl of 1 to 18 carbon atoms, which may be substituted by hydroxy, cyano or amino or halogen and which may be interrupted by oxygen, sulfur and/ or nitrogen and/ or by carbonyloxy, carbamoyl or sulfamoyl, and the radicals R and R may constitute together with the central phosphorus or nitrogen atom a heterocyclic 5- or 6-membered ring, with the proviso that the sum of all carbon atoms contained in R, R and R is at least 8 and at 'most 20, or mixtures of the compounds of formulae ('1) and (2) and subjecting the dyed material thus treated, in moist state or after an intermediate drying operation, to the action of heat 'below the softening point of the fibrous material or allowing it to dwell at room temperature or at a moderately elevated temperature, for the fixation of the dyestuff on the fiber.

2. A process as claimed in claim 1, wherein the phosphine oxides areselected from the group consisting of octyl-dimethyl-phosphine oxide, octyl-diethyl-phosphine oxide, decyl-riimethyl-phosphine oxide, decyl-methylbutyl-phosphine oxide, dodecyl-dimethyl-phosphine oxide,

dodecyl-diethyl-phosphine oxide, 'y-palmitic acid-amidemethyl-dimethyl-phosphine oxide, -palmitic' acid-amido propyl dimethyl phosphine oxide,hexyl-methyl-butylphosphine oxide and mixtures thereof. 3. A process as claimed in claim 1, wherein the amine oxides are selected from the group consisting of octyldimethyl-amine oxide, N dodecyl piperidine- N-oxide, tetra-decyl dimethyl amine oxide, coco-fatty 'acid-di methyl-amine oxide, oleoyl-arnidomethyl-dimethyl-amine oxide or hexadecylbis-(fl-hydroxy-ethyD-amine oxide and mixtures thereof.

4. A process as claimed in claim 1, wherein the phos-' phine oxide and/or amine oxide is present in an amount of from 1 to 100 g./l., calculated on the mixture of organic solvent and water.

5. A process as claimed in claim 4, wherein the phos-' phine oxide and/or amineoxide is present in an amount of from 3 to g./l., calculated on the mixture of organic solvent and water.

6. A process as claimed in claim 1, wherein said or ganic solvent is an optionally halogenated aliphatic or aromatic hydrocarbon.

7. A process as claimed in claim 6, wherein the organicv solvent is selected from the group consisting of trichloroethylene, tetrachloroethylene (perchloroethylene), trichloroethane, cloroform, carbon tetrachloride, fluorotrichloromethane and triiluoro-trichloroethane.

8. A process as claimed in claim 6, wherein said ore 10. A process as claimed in claim 6, wherein said organic solvent is a mixture of organic solvents, which may boil while forming an azeotrope. v

11. A process as claimed in claim 1, wherein the mixing ratio of organic solvent to water in the dyeing liquors or printing pastes ranges from 1-99% by volume of organic solvent to 99-1% by volume of water.

12. A process as claimed in claim 11, wherein the mixing ratio of organic solvent to water ranges from 30-98% by volume of organic solvent to 2% by volume of water.

13. A process as claimed in claim 1,, wherein the organic dyestuif is selected from the group consisting of a disperse dyestuif, a vat dyestuff, a reactive dyestulf, an acid dyestufi, a metal complex dyestuff, a chroming dyestuif, a substantive dyestuff, a leuco-ester of a vat dyestuif, a cationic dyestutf and a developing dyestuff.

14. A process as claimed in claim 1, wherein, the textile material is selected from the group consisting of awoven or knitted fabric, a combed material, a cable or a non woven article made of polyester, polyamide, polyure thane, polyacrylonitrile, cellulose-2 /2-acetate, cellulose? triacetate, polyvinyl chloride, polyvinyl alcohol, polypropylene, cellulose fibers, wool and blends of such fibrous materials.

15. A process as claimed in claim 1, wherein dyest'fulf 60 fixation by means of a heat treatment is performed by THOMAS J. HERBERT, IR., Primary Examiner Q" US. Cl. X.R. 8-.85, 171, 172, 173

tetrachloroethane, methylene chloride, 

